Method for treating the surface of an oxygen permeable hard contact lens

ABSTRACT

A method for treating the surface of an oxygen permeable hard contact lens, which comprises applying high-frequency glow discharge treatment to an oxygen permeable hard contact lens made of a copolymer consisting essentially of at least one monomer selected from the group consisting of a silicone-containing (meth)acrylate, a fluorine-containing (meth)acrylate, a silicone-containing styrene and a fluorine-containing styrene, in a gas atmosphere of at least one member selected from the group consisting of helium, neon, argon and nitrogen gas, containing substantially no oxygen.

This application is a continuation-in-part application of the application ser. No. 07/515,704 having a filing date of Apr. 27, 1990.

BACKGROUND OF THE INVENTION

1. FIELD OF THE INVENTION

The present invention relates to a method for treating the surface of an oxygen permeable hard contact lens. More particularly, it relates to a method for treating the surface of an oxygen permeable hard contact lens to give good water-wetting properties to the surface of the oxygen permeable hard contact lens.

2. DISCUSSION OF BACKGROUND

In recent years, oxygen permeable hard contact lenses made essentially of a silicone-containing (meth)acrylate and/or a fluorine-containing (meth)acrylate, have attracted an attention as hard contact lenses having excellent oxygen permeability and hardness simultaneously.

Such oxygen permeable hard contact lenses have practically satisfactory oxygen permeability and hardness as well as hydrophilic properties of the surface. However, in order to more sufficiently provide the performance as contact lenses, it is desired to further improve the affinity with tears i.e. the water-wetting properties.

As a method of giving water-wetting properties to contact lenses, it has been proposed to apply plasma treatment to the contact lenses in an oxygen-containing atmosphere to give hydrophilic properties, as disclosed in e.g. U.S. Pat. No. 4,214,014. However, such a method has a drawback that when it is employed, the material of the contact lenses tends to deteriorate and becomes brittle.

SUMMARY OF THE INVENTION

Under these circumstances, the present inventors have conducted extensive researches to develop a method for treating the surface of an oxygen permeable hard contact lens, whereby no deterioration of the material will be brought about, and the oxygen permeability and hardness can be maintained even when the treatment for giving the hydrophilic properties to the contact lens surface is applied. It has been surprisingly found for the first time that when high-frequency glow discharge is applied to the above mentioned oxygen permeable hard contact lens in a gas atmosphere of at least one member selected from the group consisting of helium, neon, argon and nitrogen gas i.e. a so-called inert gas containing substantially no oxygen, hydrophilic properties can be given while the intrinsic properties specific to the contact lens can be maintained. The present invention has been accomplished on the basis of this discovery.

Thus, the present invention provides a method for treating the surface of an oxygen permeable hard contact lens, which comprises applying high-frequency glow discharge treatment to an oxygen permeable hard contact lens made of a copolymer consisting essentially of at least one monomer selected from the group consisting of a silicone-containing (meth)acrylate, a fluorine-containing (meth)acrylate, a silicone-containing styrene and a fluorine-containing styrene, in a gas atmosphere of at least one member selected from the group consisting of helium, neon, argon and nitrogen gas, containing substantially no oxygen.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The contact lens to be treated by the surface treatment method of the present invention, is an oxygen permeable hard contact lens made of a copolymer which is composed essentially of at least one monomer selected from the group consisting of a silicone-containing (meth)acrylate, a fluorine-containing (meth)acrylate, a silicone-containing styrene and a fluorine-containing styrene, which, as mentioned above, has attracted an attention in recent years as a contact lens which can be continuously worn. With respect to the size and thickness of such a contact lens, there is no particular restriction. A contact lens of any size and thickness may be treated by the method of the present invention so long as it is of the type normally worn on an eye.

In the present invention, the atmosphere for the high frequency glow discharge treatment is a gas atmosphere of at least one member selected from the group consisting of helium, neon, argon and nitrogen gas, which contains substantially no oxygen. The reason why such an atmosphere should not contain oxygen, is that if the treatment is conducted in the presence of oxygen, the contact lens tends to be brittle. Among the above mentioned gases helium, neon and argon are particularly preferred, since they do not deteriorate the lens material even when the treatment is applied to the contact lens surface for a long period of time. The pressure of the gas atmosphere is usually within a range of from 0.01 to 5.0 Torr.

Referring to an example of the conditions for the high-frequency glow discharge treatment, the frequency for the high-frequency glow discharge is, for example, usually about 13.56 MHz, and the discharge output is usually from 10 to 1,000 W. The discharge treating time is usually from 10 seconds to 20 minutes. However, it should be understood that the present invention is not limited to such specific conditions.

The surface treatment method of the present invention is conducted by means of a reduced pressure container having an inlet for introducing an inert gas such as helium, neon, argon or nitrogen gas and an evacuating means to evacuate the container to a predetermined reduced pressure level. A contact lens is mounted between an anode and a cathode, the container is then maintained under a predetermined reduced pressure state, and then predetermined high frequency glow discharge treatment is applied between the anode and the cathode. The contact lens with its surface thus treated, has hydrophilic properties given while the oxygen permeability and the hardness of the contact lens itself are maintained.

Now, the method for treating the surface of an oxygen permeable hard contact lens according to the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples.

In the following Examples, "parts" means "parts by weight" unless otherwise specified.

EXAMPLE 1

As the oxygen permeable hard contact lens, a contact lens (hereinafter referred to simple as CL-A) composed of 35 parts of tris(trimethylsiloxy)silylpropyl methacrylate, 40 parts of trifluoroethyl methacrylate, 5 parts of methyl methacrylate and 6 parts of ethylene glycol dimethacrylate, a contact lens (hereinafter referred to simply as CL-B) composed of 45 parts of tris(trimethylsiloxy)silylpropyl methacrylate, 40 parts of trifluoroethyl methacrylate, 4 parts of methyl methacrylate, 5 parts of methacrylic acid and 6 parts of ethylene glycol dimethacrylate, a contact lens (hereinafter referred to simply as CL-C) composed of 60 parts of tris(trimethylsiloxy)silylpropyl methacrylate, 25 parts of hexafluoroisopropyl methacrylate, 5 parts of N-vinyl pyrrolidone, 5 parts of methacrylic acid and 5 parts of ethylene glycol dimethacrylate, a contact lens (hereinafter referred to simply as CL-D) composed of 46 parts of tris(trimethylsiloxysilyl)styrene, 54 parts of hexafluorisopropyl methacrylate, 6 parts of vinyl benzyl methacrylate, 4 parts of methacrylic acid, 5 parts of N-vinyl pyrrolidone, or a contact lens (hereinafter referred to simply as CL-E) composed of 52 parts of tris(trimethylsiloxysilyl)styrene, 48 parts of p-[2-(nonafluorobutyl)ethyldimethyl]silyl styrene, 6 parts of vinyl benzyl methacrylate, 5 parts of methacrylic acid, 6 parts of N-vinyl pyrrolidone, was employed.

Further, helium, argon and nitrogen gas used, were respectively, passed through a concentrated pyrogallol solution as an oxygen absorber and then through a silica gel column for drying.

Then, CL-A, CL-B, CL-C, CL-D or CL-E was subjected to glow discharge treatment under the conditions as identified in Table 1, and the change in the contact angle before and after the treatment was examined. The results are shown in Table 1.

                                      TABLE 1                                      __________________________________________________________________________                  Pressure of   Glow Contact angle (degrees)                        Test                                                                              Type of                                                                             Type of                                                                             gas atmosphere                                                                               discharge                                                                           Before                                                                               After                                    No.                                                                               lens gas  (Torr)  Output (W)                                                                           time treatment                                                                            treatment                                __________________________________________________________________________      1 CL-A N.sub.2                                                                             0.8     50    10                                                                               sec.                                                                              101   67                                        2 CL-A N.sub.2                                                                             0.8     50    3 min.                                                                              101   27                                        3 CL-A N.sub.2                                                                             0.8     50    15                                                                               min.                                                                              101   31                                        4 CL-B N.sub.2                                                                             0.8     50    10                                                                               sec.                                                                              100   75                                        5 CL-B N.sub.2                                                                             0.8     50    3 min.                                                                              100   30                                        6 CL-B N.sub.2                                                                             0.8     50    15                                                                               min.                                                                              100   32                                        7 CL-C N.sub.2                                                                             0.8     50    10                                                                               sec.                                                                              104   78                                        8 CL-C N.sub.2                                                                             0.8     50    3 min.                                                                              104   30                                        9 CL-C N.sub.2                                                                             0.8     50    15                                                                               min.                                                                              104   31                                       10 CL-A He   0.8     50    10                                                                               sec.                                                                              101   69                                       11 CL-A He   0.8     50    3 min.                                                                              101   40                                       12 CL-A He   0.8     50    10                                                                               min.                                                                              101   36                                       13 CL-B He   0.8     50    10                                                                               sec.                                                                              100   72                                       14 CL-B He   0.8     50    3 min.                                                                              100   33                                       15 CL-B He   0.8     50    10                                                                               min.                                                                              100   38                                       16 CL-C He   0.8     50    10                                                                               sec.                                                                              104   64                                       17 CL-C He   0.8     50    3 min.                                                                              104   32                                       18 CL-C He   0.8     50    10                                                                               min.                                                                              104   38                                       19 CL-A Ar   0.8     50    10                                                                               sec.                                                                              101   66                                       20 CL-A Ar   0.8     50    3 min.                                                                              101   36                                       21 CL-A Ar   0.8     50    15                                                                               min.                                                                              101   36                                       22 CL-B Ar   0.8     50    10                                                                               sec.                                                                              100   76                                       23 CL-B Ar   0.8     50    3 min.                                                                              100   35                                       24 CL-B Ar   0.8     50    15                                                                               min.                                                                              100   36                                       25 CL-C Ar   0.8     50    10                                                                               sec.                                                                              104   80                                       26 CL-C Ar   0.8     50    3 min.                                                                              104   33                                       27 CL-C Ar   0.8     50    15                                                                               min.                                                                              104   34                                       28 CL-B Ar   1.2     50    5 min.                                                                              100   35                                       29 CL-D N.sub.2                                                                             0.8     50    3 min                                                                               104   15                                       30 CL-E N.sub.2                                                                             0.8     50    3 min.                                                                               97   16                                       31 CL-D He   0.8     50    3 min.                                                                              104   18                                       32 CL-E He   0.8     50    3 min.                                                                               97   17                                       33 CL-D Ar   0.8     50    3 min.                                                                              104   20                                       34 CL-E Ar   0.8     50    3 min.                                                                               97   19                                       35 CL-D O.sub.2                                                                             0.8     50    3 min.                                                                              104   19                                       36 CL-E O.sub.2                                                                             0.8     50    3 min.                                                                               97   18                                       37 CL-D He   0.8     50    15                                                                               min.                                                                              104   18                                       38 CL-E He   0.8     50    15                                                                               min.                                                                               97   20                                       39 CL-D O.sub.2                                                                             0.8     50    15                                                                               min.                                                                              104   19                                       40 CL-E O.sub.2                                                                             0.8     50    15                                                                               min.                                                                               97   20                                       __________________________________________________________________________

EXAMPLE 2

As the contact lens, CL-C and CL-D were used, and with respect to helium, argon and nitrogen gas used, the same treatment as in Example 1 was applied so that the gas used, contained substantially no oxygen. The glow discharge treatment was applied in the same manner as in Example 1 in the gas atmosphere as identified in Table 2 (provided that the pressure of the gas atmosphere was 0.8 Torr) under such condition that the output was 50 W and the glow discharge time was 15 minutes, and the change in the contact angle before and after the treatment was examined. The results are in Table 2.

Then, the surface condition of the contact lens before and after the treatment was observed by a microscope (20 magnifications). Further, while fixing the peripheral portion of the contact lens, a penetrating needle having a forward end diameter of 2 mm (2 R) was pressed against the center of the lens, and the load (kg) at the time of the breakage of the contact lens was measured, whereby a value obtained by dividing the load by the thickness at the center of the lens, was taken as the lens strength. The results are shown also in Table 2.

                                      TABLE 2                                      __________________________________________________________________________                     Contact angle                                                                            Surface condition                                                                         Lens strength                                             (degrees) of lens    (kg/mm)                                         Type of                                                                             Type of                                                                             Before                                                                              After                                                                               Before                                                                              After Before                                                                              After                                Test No.                                                                             lens gas  treatment                                                                           treatment                                                                           treatment                                                                           treatment                                                                            treatment                                                                           treatment                            __________________________________________________________________________     1     CL-C He   104  32   Good*                                                                               No change                                                                            8.0  7.6                                  2     CL-C Ar   104  34   Good*                                                                               No change                                                                            8.0  7.2                                  3     CL-C N.sub.2                                                                             104  31   Good*                                                                               No change                                                                            8.0  7.4                                  Compara-                                                                             CL-C O.sub.2                                                                             104  31   Good*                                                                               Fine  8.0  0.4                                  tive Test                      cracks                                          No. 1                          formed                                          4     CL-D He   104  18   Good*                                                                               No change                                                                            3.4  3.0                                  Compara-                                                                             CL-D O.sub.2                                                                             104  20   Good*                                                                               Fine  3.4  0.9                                  tive Test                      cracks                                          No. 2                          formed                                          __________________________________________________________________________      *Smooth surface with no cracks or scratches                              

From the results of Tables 1 and 2, it is apparent that according to the method for treating the surface of an oxygen permeable hard contact lens of the present invention, hydrophilic properties can be given to the surface of the contact lens without bringing about a deterioration of the material of the contact lens or lowering the hardness of the contact lens.

Thus, the method for treating the surface of an oxygen permeable hard contact lens of the present invention provides an effect of giving water-wetting properties to the surface while maintaining the oxygen permeability and the hardness without bringing about a deterioration of the material of the contact lens. 

What is claimed is:
 1. A method for treating the surface of an oxygen permeable hard contact lens, which comprises applying high-frequency glow discharge treatment to an oxygen permeable hard contact lens made of a copolymer consisting essentially of at least one monomer selected from the group consisting of a silicone-containing (meth)acrylate, a fluorine-containing (meth)acrylate, a silicone-containing styrene and a fluorine-containing styrene, in a gas atmosphere of at least one member selected from the group consisting of helium, neon, argon and nitrogen gas, containing substantially no oxygen.
 2. The method according to claim 1, wherein the gas atmosphere is made of at least one member selected from the group consisting of helium, neon and argon.
 3. The method according to claim 1, wherein the gas atmosphere has a pressure within a range of from 0.01 to 5.0 Torr.
 4. The method according to claim 1, wherein the high-frequency glow discharge treatment is conducted with a frequency of about 13.56 MHz.
 5. The method according to claim 1, wherein the high-frequency glow discharge treatment is conducted at a discharge output of from 10 to 1,000 W for from 10 seconds to 20 minutes.
 6. The method of claim 1, wherein said copolymer consists essentially of a silicone-containing (meth)acrylate monomer and a fluorine-containing (meth)acrylate monmer.
 7. The method of claim 1, wherein said copolymer consists essentially of a silicone-containing styrene monomer and a fluorine-containing (meth)acrylate monomer.
 8. The method of claim 1, wherein said copolymer consists essentially of a silicone-containing styrene monomer and a fluorine-containing styrene monomer.
 9. The method of claim 1, wherein said copolymer consists essentially of a silicone-containing (meth)acrylate monomer and a fluorine-containing styrene monomer.
 10. The method of claim 1, wherein said copolymer consists essentially of a silicone-containing (meth)acrylate monomer and a silicone-containing styrene monomer and a fluorine-containing (meth)acrylate monomer.
 11. In a method for treating the surface of an oxygen permeable hard contact lens made of a copolymer consisting essentially of at least one monomer selected from the group consisting of a silicon-containing (meth)acrylate, a fluorine-containing (meth)acrylate, a silicon-containing styrene and a fluorine-containing styrene to give said surface improved water-wetting properties, the improvement comprising applying high-frequency flow discharge treatment to said hard contact lens in a gas atmosphere of at least one member selected from the group consisting of helim, neon, argon and nitrogen gas, containing substantially no oxygen. 